Process for hydrocarbon conversion



Marh,1946 'K HHAC'HMUTH" 2,396,173 y PROCESS FOR HYDBocARBoNoNvERsIoN UNI-reo,s-TArEs --N--PATENT l irnocassFoRfnYDnocAnnoNooNvERsroNf "1' Karl H Hachrnut-h, liartiesivillgalE assignor ,A l -v to Phillips Petroleum Companma corporation s.

ofDeiaware A' 1 Application octal-ier" vtrivia; s rial. .No..isnloe y v157 `claimt- (chase-e335), l,

catalyst chamber along` with theiisornerizaticn products This aluminumchloride vis*deposited,in"A` the transfer lines, valves', and other parts ,of the equipment, particularly at points of lower tem` l This invention relates to the'removal of metal halides, especially active m'etal halidesof theV Friedel-Crafts type, 'from admixture with hydro-- carbons. More particularly fit relates .to lthe re#-r moval of such metal halides as yaluminum chloride and' thef like .from solution-cr"suspension. insubstantially saturated hydrocarbons.. It has yparticular applicability'to `noli-tiesiructive hydrocarbonaconversionsuci1izm'girriedei-Crafts `.type

metal `halide catalystsfwherein traces or such catalyst are carried over thel saturated hydro-VV-`V carbon effluents.

Of great commercial interest lat the present I time are the isomerizatio'nfand alkylationof lowboiling hydroc`arbons,` Aparticularly 'members of the paraffin `series such' as 'the butan'es and pentanes.W In vthese-,reactionsf;a simple chemical, change is feffected underrelativelyv mildV c ondif tions: in the case of .iso`meriz:a.tion`,v ajchange in carbon skeleton *without change'in r'iumber of carbon atoms ccursand in'jtheca'se of alkyla v tion, the-direct union of two molecules, 'such asv` an isoparaflin and an' oleiin',v occurs tolproduce'a highery molecular weight 'saturated hydrocarbon.

These reactions are known to be catalyzed insa greater or lesser extent-bythe so-called Friedell Crafts catalysts, among Y' the better known of which may be .mentionedY aluminum', chloride, aluminum lbromide, boron iiorid e',. zinc chloride,"y ferric chloride, antimony trii'i'uo`ride,` and'other polyvalent metal halides. Aluminum chloridev has as to date received/the`vv greatest commercial g 1 acceptance due to its activity;4 relatively'low cost., and availability. Accordingly,y because vof'its imA 35 admixture vwith substantially saturated hifciro-yjfA carbons by reacting unsaturatedhydrocarbonsgj v ksuch as monoolefins', diolelns,v acetylenesfetcg with said metal halide to form a metal halide- ,f hydrocarbony sludge which is readily separable" 740 as a separate phase; fromy either gaseous vor; 5 n liquid saturated hydrocarbons. vAccording'to my invention; I- incorporate said metal halidei in such a sludge, :and separate the saturated i hydro'car-v portance, and -for i the sake yof convenience Isha'll y v describe my invention withzparticular referenceI"- to the isomerizationfof normal butane to yisoplication of theinvention tootherwsiniilar. hydro-V carboncconversions, using aluminum chloride or other Friedel-Crafts typemetal'halide catalysts,

in which substantially fsaturatedf; hydrocarbon eiuents are produced, will be' apparenttozthose skilled in the'art in view lofthe detailed disclosure to follow.

Aluminum chloride andfjotherfV lriedelfCrarts catalysts are relativelyv volatile, and kmay also exhibitiappreciable solubility infliquidffhydro carbons. `Thisvolatilltyand solubility give rise' to s erious operatingz'diiilculties; particularly in continuous processes'. The .'isomerizationv of butane may be carried out'with thehydrocarbon, in the liquid or gaseousphas'e,the/ latter being? 1 morev often used. SmalLbutappreciable quan--y titles of aluminumchloride are carried out of the 5 -perature` than that obtainingin'f 'theA lcatalyst 1 6 uselof such products. y

lysts'z" further object istoremove from satufothersimilar metal halide may be' 'removediirom bonsfrom the sludge. The'metal halidemaybe 45v incorporated inthe sludgein the free-state;for' in the combined metal halide-hydrocarbon sludgev l fornnbut in veither "cas'e the metal halide isi-e-`U vacted with unsaturated hydrocarbons prior-450,y 'l' l during, or after its incorporation intosaidjsludge.; -50 It is,l preferable thatfsuflicient unsaturatembe i providedy to free such sludge from'y ncombined metal halide,`or at 'leastt'o reducethe concentra-, tiony below the level at-whichit ifsfobjectionable in subsequent processing.

M Oleilrls or other unsaturatesl utilizedthisv chamber; These deposits ofvalumi'num chloride L require frequent shut down to enable their re-jv moval, ywith consequent 4loss of rplant 'capacitYf and. .the expenditure of-J otherwise unnecessary*` lo' labor.- The corrosivefeffects'-of@the alurriinum' l chloride Iare alsoy frequently serious, particularly in the valvesand pumps. It is'also difcult tooo-1 1 tain Aproducts of the processl free-fromalumin'um Y chloridelfwhich may -interferewith subsequent Itis an objeotlof this invention'to provide `for the-removal of active metalhaIideS-rOm adin'ixfvv turefwith hydrocarbons.; A- further object isto'rf provide .improvements in `the non-destructive .Y 20con'version of relatively .low-fboiling';hydrocarf-"f bons `with FriedeleCrafts type metal halide catarated ,hydrocarbon eiiluents from .the catalyst zonet-,he volatilized and/ or dissolved metalghalide f 25 lcataly'rstcontained. therein, and thus avoid foul ing" of f equipment through' whichl such eiuents L i subsequently pass. A further l'object is tofproyide. a y.method of "freeing substantially sza,tu1,ate:l v hydrocarbons from aluminum chloride vaporized, yj 3 0 dissolved, and/or suspended therein. Many yother objects as well as`- advantages `of"'-tl1is invention will be apparent fromthe present .disclosure.;y l. `I 'have 'found that free'aluminumochloridev orv invention act to sludge the aluminum chloride saturated hydrocarbons beingadmitted to the or other metal halide, and a portion of the oleprocess either intermittently or continuously. uns may also` frequently react to form olennic Referring now to Figure 1,dry gaseous normal polymers, or if the saturated hydrocarbons unbutane, either pure or containing minor amounts dergoing treatment contain alkylatable hydro- 5 of isobutane and/or lighter gases suchaspropane, carbons, may react with the same to give alkylaf along with activating amounts of anhydrous hy tion products. `Such' higher molecular weight drogen chloride' or other activating agent, is inlurdrocarbons so formed comprising 4polymers troduced into the bottom of catalyst chamber IA and/or alkylate, may be recoveredl as valuable through conduit 2A. Thehydrogen chloride may products land utilized in aviation gasoline blends i vbe introduced into the reaction zone in other ways or otherwise as desired. l if' desired, and in mostcases will comprise from 'I'he amount` of unsaturates required is ordiv v3 to l5 mol per cent of the feed.` Chamber IA is narily very small las compared with the volume of operatedk at a pressure of 100- to 150 pounds per hydlOeoIbOI-'IS beillg treated. Frequently leSS than' squarey inch gage and a temperature of about 200 one per cent offunsaturates is sufficient, and 15. F. The feed being introduced through conduit more than a few per cent, is seldomv necessarv.A I n :Ais heated torthe proper temperature by means some cases a considerable excess of unsaturates not shown 1f necessary, the butane ls de'hymay be used, and the unreaeted portion thereof drated before introduction to the catalyst. The subsequently recovered if desired. vSuch recovery i 'now rate wlll generally be between baut 0,1 to may beirom the saturated hydrocarbons by frac- 2o 2.o liquid vol'umes orhvdrocsrbon reed per volume tionation or the like, or in certain methods of of catalyst /ohailziber per` hour.r Catalyst chamoperating.v to be described inv detail below. the berlA contoinsf'pieces oi solid anhydrous alumiunsaturates are not mixed directlyy with the.'y num chloride of about 20 mesh or larger, or may saturates, yand any excess is thus more readily (gl-,malinv sultable supported aluminum emol-lds, reeoveredf` d 25 catalysts known to the srt.-

My invention 1S especially applicable to Viso- The gaseous eiiiuent :rom chamber IA which merization of low-boiling saturated `hydrocarcomprises isobutane,` normal butane, hydrogen l bons such as normal butane, normal pentane, chloride, lighter gaseslandsmgll amounts 01' V015.. normal hexane. ete toV form` the corresponding tilized aluminum ehioride'ieav'es the top or.chem. isoparamns. 'It is also quite applicable to the 30 ber-IA via conduit i. Spentalumin'um chloride, alkylatioh of alkylatsbie hydrocarbons, especially which usually `roriliiisis a sludge, may be removed the relatively .low-boiling:isoparailins,l with al-- from chamber IA eithercontinuouslyor interkyla'ting agents. low-boiling oleins such as mittently through conduit I.v .f propylene, butylenes, and pentenes being ordi- Unsaturated hydrocarbons, for example propylused. In such an alkylation. although oleene' or butylenes or' a :mixture containing the iins are present in the reaction zone proper, the same, are injected into admixture with the gases reaction zone emuent or alkylate is .often sub-l in conduit 3, as `through lineI. .'I'hese unsatustantially saturated, and appreciable quantities rated hydrocarbons react rapidly lwith the alumiof the metal halidecataiyst' are to be found diso y,

,solved or suspended in the emuent. 'The catalyst t0 form en *,elumlum ohlorideshydrocarbon may he used in the reaction zone either as a solid Sludge @111181111118 substantially no free or uncomor as a slurry` compl-mns considerable amouts bined aluminum chloride. At least sumcient unoi metal hande dissolved end/or suspended in selurelee erepl'evided te11eteubetentie1lv eomliquid hydrocarbons or other suitable liquids. 45- plete remOvel 0f the' l4111111111111 .Chlerlde es sludge. The carried-over metal halide may appear in the n an excess is adde' it may later be removed reaction zone eiiiuents inthe vaporized form. or fmm the lsomenztmnproduct by fractionation dissolved orgsuspended m nquidemuents or other suitable means if desired. Aportion of Temperature and pressure conditions used in the wenns may llte some '0f the isobutone, the hydrocarbon conversions'rei'erred to are mild 50 nd fthe Smau amo t of heaver'isopammns thus so that no' extensive decomposition reactions ocblxgg may be subsequently separated from the cur, the exact conditionsbeing readily chosen byone skilled in the art for the particular isomeriza- The material in une 3 passes into separamr 5 tion, alkylationpor other reaction involved In Where the mamme sludge dm ut 0m the most cases the temperatures 1n the s1ud8e for'm 55 gases and is removed via conduitl. The isomer- Y lng zone will be similar to thoselin the reaction ization e-muents thutree-d of sludge .and ammi' zone' but maybe appreciably lower J d 4num chloride\pass out from separator o to fur- Metal handemydrarbon sludge formed m ther treatment, separation; or the'like via conduit carrying out my invention may be sent to sludge'y Y t' n desired' sepmwr may be filled with any disposal, to a process for recovery of metal halide suitable type of packing t0 am in collecting and therefmm, orto other use u desired. y separating the sludge from the hydrocarbon The accompanying drawing and description stream' Bud?, as rksfmchls, ma] 0T the likethereof are provided for. the mehr bettel, f In case the conversion in chamber IA is carried illustrating and-exemplifying the invention, and 55 out in the liquid Phmredul catalyst carried A show diii'erent ways of applying the invention to' e mtb-V 5013130111 the hydmwbon liquids reacts a butane isomerization process. Numerous other with the added unsetul'ted hydrel'bODs to form modmctions msy be used, f6,- rrylng out val-l-' a sludge vwhich is insoluble in the iiquid'hydrof ous reactions, by following the teachings of this ClbOnS end thus readily separated-In unit 6 disclosure, and no particular llmltatlons are as a phase separatefromthe hydrocarbons. therefore implied. Figure 1 shows in diagram- The emllenli from Seplotor I comprise unconmatic form one suitable arrangement oi' appara.- vetted normal butane,( isobutane produced inthe tus, and Figure 2 shows another suitable arrangef process, i traces of nvev-carbon-atom and heavier meritl of apparatus wherein one or more sludgel hydrocarbons, f hydrogenl chloride.V and minor contacting chambers may be used, with the un- ,75 amounts o1' other gases lighter' than isobutane arating or other steps known to the art.` These.

usually include separation of hydrogen chloride,

' propane, and unconverted normal butane, which are recycled to catalyst chamber IA. Variousl other expedients which are known to the art may of course be'utllized as particular'circumstances indicate.

' The' eiliuents in line 8, due to the action of the added oleilns, are substantially free from residual aluminum chloride, which makes possible their further treatment without encountering the troublesome condensation of aluminum chloride in lines and equipment as discussed hereinabove.

'assura aluminum chloride vapors inthe stream to form sludge and/or the aluminum chloride vapors may be absorbed from the stream by the sludge ilowing over the packing in .chamber 9, with the unsaturates reacting with the thus absorbed aluminum chloride to form additional amounts of an inactive sludge. Probably both such actions occur, the extent of each depending on, amongother things, the length of time'the unsaturates remain mixed with the valuminum chloride-bearing hydrocarbon gases before the sludge in chamber 9 is contacted. At any rate, the aluminumchlo ride becomes incorporated in the sludge, and reacts with added unsaturates to form sludge, and the hydrocarbons are freed of the residual aluminum chloride by such reaction. 4

The unsaturates may be added intermittently rather than continuously. It has been found In Figure 2, the butane fees vemersicatalyst chamber IA, which contains the aluminum chloride catalyst, through conduit 2A, and conversion products, including small *amounts of aluminum chloride, exit through line 3. Line 4 is providedV for removing any sludge which accumulates in chamber IA. Two contacting chambers, 9 and I Il, are shown in Figure 2. These `chambers are packed with ceramic rings or other suitable contact material to promote intimate contact between hydrocarbons and sludge. Other devices adapted to achieve this contact may of course be used, but I have found thisr particular type of chamber to be especially advantageous.

In one modification of my invention, only one y such chamber is used. In this case, the' effluents in conduit 3 are passed via line I I into the bottom of chamber 9. Unsaturated hydrocarbons are Il as shown or directly into chamber s, Ifor reaction with the aluminumchloridecarried over from catalyst chamber IA. Sludge formed by the action of the oleflns or other unsaturates on the aluminum chloride separates out onto the packing in chamber 9. This sludge runs down over the packing, presenting a highly extended surface to the hydrocarbons, and is removed from' the bottom of chamber sthrough line I5. It is `recycled via line I1 by pumping, pressuring, orA other means, and introduced into the top oi' cham# ber 9, wherein it again flows down over the packing. Excess sludge is drawn of! through line 1A.l

Isomerization eiliuents iree from aluminum chloride leave chamber! via conduits I9 and 2i, and

pass to separation means indicated diagrammati-v cally at 32, wherein the product, in this case isobutane, is separatedand'recovered vialine 33,

while unconverted material, such as normal bu'-` tane, and catalyst promoter, suchas HCI, are

recycled to the catalyst chamber via lines 3l. lo

and ll'. a

The sludge on the packing in chamber I may have a dual function. It aids in separating from the hydrocarbons additional sludge formed by reaction of oleilns with aluminum chloride. It also has a very high absorptive power for aluminum chloride itself, and acts to absorb aluminum chloride from vthe butane vapors.y In casegthe olenns or other unsaturates from line 5 are added vcontinuously to the stream ci.' catalyst chamber eiiluents, these unsaturates may react with the passed from conduit I5 either into line II via line l that when this is done, the laluminum chloride-- hydrocarbon sludge will'readily absorb the aluminum chloride vapors evenv inf the absence of the unsaturates.

aluminum chloride' dissolvedin -the sludge in However, as.. theamount of f free creases, the readiness with which additional aluminum chloridev is dissolved .is decreased. 'I'hus after a period of operation thel sludge becomes activated with free aluminum chloride to such an extent that not `all of the aluminum chloride carried over by the eiiluent stream from the conversion zone is' absorbed. When this happens, or before such condition is reached, the unsaturates are introduced to react with the aluminum chloride to ensure its completeremoval from the hydrocarbons. Sufilcient unsaturates -are used for a suillcient length of time to ensurev that the sludge is substantially spent or at least to ensure that the Vsludge is kept deactivated to or below la'. satisfactory value at all times. After suiilcient unsaturates have been thus introduced, the sytem mayfagain be operated for a period of time vwithout the addition of unsaturates.'

l Depending upon conditions in chamber l, heavyv polymersor alkylate formed by reaction of the olens alone or with isobutane, may separate-out in chamber 9 asa liquid and be removed through line 1A or otherwise, or they may remain in thel `vaporstate and pass out through line 2|.

In caseit is undesirable to addv unsaturates to the isomerization efiiuents, the two chambers, 0 and III, may be utilized. In'such case the cata-l -lyst chamber eiiiuents are passed through chamber 9 in the absence of added oleilns until the amount of uncombined aluminum` chloride in the sludge is so great that absorption is not 'taking place to the desired extent. At such time, the

ow is switched to chamber I0, in which the ab-` sorption of aluminum chloridev in sludge continues. Meanwhile, unsaturates are passed through chamber 9 to react with the absorbed @23 in line Il and valve 21 in line 2| are open allowing reaction zone eiiluents from line 3 to aluminum chloride therein andV place the sludge in condition for further eil'ective absorption. When the sludge in chamber III loses its absorp- .tive capacity to too great an extent, the flow of butane isomerization eilluents is again returned to chamber 9 while unsaturates are passed through chamberk I0.

In theilrst cycle of such an operation valve flow through chamber y'9, while valve 24 in line I2 and valve 28 in line20 are closed lto prevent such flowA through chamber". Valve 2B in line Il and valve Il) in line II are open, allowing unsaturates from line I to ow through chamber I 0 to .deactivate'the sludge therein. t'while valve 25 in line I3 and valve 29 in line 22 are closed to prevent access of unsaturates to chamber 9. The flow of unsaturates through chamber I may be stopped by closing valves 26 and 30 before it is necessary to put chamber I0 back into service for treating isomerization zone effluents.

When the sludge in chamber 9 becomes too activated with absorbed uncombined aluminum chloride, valves 26 and 30 are closed if they are not already closed, valves 24 and 28 are opened to permit passage of material from conduit 3 through chamber I0, and valves 23 and 21 are closed to stop such passage through chamber 9. Unsaturates are then passed through chamber 9 via lines I3 and 22 by opening valves 25 and 29. Sludge is circulated through chamber l0 by means of conduits I 6 and t8, and excess sludge is removed via conduit 1B. A certain amount of polymerization of the unsaturated hydrocarbons used in the deactivation step will occur, and if desired these polymerization products can be recovered from the unsaturated hydrocarbon effluent stream from the deactivation step or separated as liquids from the sludge in suitable manner.

The cycle described may be continued indefinitely, with one of the two chambers always being on-stream for absorption of aluminum chloride, while the other is being treated with unsaturates to sludge the free aluminum chloride therein, or is standing by ready for service. More than two chambers may be used for this type of operation if desired, as will be well understood by those skilled in the art.

The type of unsaturated hydrocarbons used in any particular modification of this invention will depend upon the availability of such unsaturated hydrocarbons and upon the nature of the saturated hydrocarbons being treated. Frequently the normally gaseous olens are convenient to use, since their degree of unsaturation per unit of weight is high. I have also found that liquid oleflns are useful in my process; for example, gaseous saturated hydrocarbons containing residual aluminum chloride may be bubbled through a body of heavy liquid olenic polymers, which may be obtained as by-product from other hydrocarbon conversion processes. If desired, such heavy polymers may be recirculated with the sludge in packed chambers as described above.

These and other modifications are within the scope of my invention, which is to be limited only by the appended claims.

I claim:

1. In a hydrocarbon conversion process utilizing a Friedel-Crafts type metal halide catalyst wherein elluent substantially saturated hydrocarbons contain residual metal halide, the method of freeing said eliluent hydrocarbons from said metal halide which comprises contacting said effluent hydrocarbons with a metal halide-hydrocarbon sludge to effect removal of said metal halide by absorption in said sludge, stopping the contacting of said eilluents with said sludge whenever the concentration of free metal halide in said sludge becomes sufciently high to prevent the absorption of additional amounts of said metal halide from said eilluents to a desired extent, contacting unsaturated hydrocarbons with said sludge until the concentration of free metal halide in said sludge is diminished to a desired extent, and again contacting said sludge with said eilluents to effect absorption of metal halide therefrom.

2. A continuous process for the isomerization of normal butane which comprises continuously passing an anhydrous gaseous mixture comprising a major proportion of normal butane admixed with a minor proportion of hydrogen chloride into contact with a solid anhydrous aluminum chloride catalyst at conditions of temperature, pressure, and contact time to give a substantial yield of isobutane, passing gases from said contacting into contact with a first increment of aluminum chloride-hydrocarbon sludge under conditions favoring absorption of aluminum chloride vapors from said gases by said sludge, recovering' isobutane and recycling hydrogen chloride and unconverted normal butane to contact with said catalyst, periodically changing the ilow of gases from contact with said first increment of' said sludge into contact with a second increment of said sludge, contacting low-boiling monooleflns with said first increment of sludge to react with absorbed aluminum chloride therein, thus forming additional sludge, and then reestablishing the flow of gases into contact with said first increment of sludge to effect further absorption of said aluminum chloride vapors from said gases.

3. A process for conversion of low-boiling hydrocarbons with a Friedel-Crafts type metal halide catalyst, which comprises passing a stream of low-boiling hydrocarbons in contact with such catalyst under' conditions to effect the desired conversion and whereby some metal halide becomes incorporated in said stream, passing the resulting stream in vapor phase in contact with a liquid metal halide-hydrocarbon sludge to absorb said metal halide from said stream, intermittently introducing into contact with said stream and said sludge an excess of a liquid oleinic polymer to react with said metal halide and to maintain the concentration of uncombined metal halide in said sludge at a low value conducive to allowing further absorption of metal halide from said stream, and recovering from said stream conversion products substantially free from metal halide.

4. In a hydrocarbon conversion process utilizing a Friedel-Crafts type metal halide catalyst wherein eiliuent substantially saturated hydrocarbons contain residual metal halide, the method of freeing said eilluent hydrocarbons from said metal halide which comprises contacting said effluent hydrocarbons with a. metal halide-hydrocarbon sludge to effect removal of said metal halide by absorption in said sludge, and whenever the concentration of free metal halide in said sludge becomes sufllciently high to prevent the absorption of additional amounts of said metal halide from said effluents to a desired extent, contacting unsaturated hydrocarbons with said sludge until the concentration of free metal halide in -said sludge is diminished to a desired extent.

5. A process according to claim 4 in which said metal halide is an aluminum halide.

6. A process according to claim 4 in which said metal halide is aluminum chloride.

'7. A process according to claim 4 in which said sludge is continuously circulated over an inert packing material thus presenting an extended surface of sludge to said hydrocarbons.

8. In a hydrocarbon conversion process utilizing a Friedel-Crafts type metal halide catalyst wherein eflluent substantially saturated hydrocarbons contain residual metal halide, the method of freeing said eilluent hydrocarbons from said metal halide which comprises contacting said efnuent hydrocarbons with ametal halide-hydrovcarbon sludgeto-eiiect removalk oi' said metal halide by absorption in vsaid sludge, and 'introduc- .ing unsaturated hydrocarbons into contact with said sludge rto, react with thus-absorbed metaly halide,` at leastsa ypartei said removal being accomplished in the absence of thus introduced unsaturated hydrocarbons.

is. A process .according so. claim 12' in which lsaid unsaturated hydrocarbons comprise oleiins.

16. In the removal of Friedel-Crafts type metalA halides 'from hydrocarbon vapors comprising' es- 9. A process according to claim 8 which said conversion is an isomerization' reaction.

10. A processsaccording to claim l8 in `which 4, said conversion is an alkylation reaction. v 11. A process according to claim 8 in which said unsaturated hydrocarbons are intermittently introduced into a zonewherein said eiliuent hydrocarbons are continuously contacting said sludge.

12. A method of removinguncombined Friedel'- Crafts type metal halide from substantially saturated hydrocarbons containing ythe same, which y comprises .passing such hydrocarbons in the.y vapor phase in contact with a liquid metal halide-hydrocarbon sludge under conditions vfavoring absorptionr of said metal halideby said sludge,

end maintaining the concentration of uncombined metalhalide in said sludge below a value so high as to prevent absorption of said metal ,y halide from said hydrocarbons to a desired eirtent, by reacting said metal halide with unsatuf rated hydrocarbons. f

13. The method of claim 12 in which said sat-v saturated hydrocarbons, the improve-Uy y ment which comprises passing such vapors containing such `metal halide in contact with liquid oleiinic` polymers, therebyr reacting said metal halide with said polymers to form a sludge, and separating from said polymers and said sludge miydrocarbon vvapors thus freed of said metal 17. A continuous process for the conversion V hydrocarbons which comprises continuously pass` v ing a stream of hydrocarbon material to be con- .verted through a vcatalyst zone containing 'a Friedel-Craftstype metal halide catalyst at ccm#` version conditions, circulatingv separate 'incre-J y ments fof metal halide-hydrocarbon sludge through each oi! at least two contacting zones-v` adapted to enect intimate contact e betweeny y sludge and hydrocarbons, passing a stream of substantially saturated hydrocarbons obtained.` fromsaid catalyst zone and containing residual metal halide through one of said contacting zones under conditions adapted to eiIect removal of said l residual metal halide fromsaid stream' by ab- 'f sorption inl said sludge,l passing a stream of unsaturated hydrocarbons. through another oi said urated hydrocarbonsare passed in the vapor phase through a chamber containing solid icon-v *y tact material in countercurrent contact with said sludge and with liquid oleiinicpolymers, 'andin which said sludge and-said polymers are recirculated over said contact material insaid chamber.

14. A process according to claim 12in which said substantially saturated hydrocarbons coniprisel relativelyk low-boiling paramns.

on-stream for ysaid saturated hydrocarbons land on-stream for said unsaturated hydrocarbons.v

KARL H. mcnMU'rn. 

